WO2000015632A1 - Derives de thiopyrone et leur utilisation comme pesticides - Google Patents

Derives de thiopyrone et leur utilisation comme pesticides Download PDF

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Publication number
WO2000015632A1
WO2000015632A1 PCT/EP1999/006475 EP9906475W WO0015632A1 WO 2000015632 A1 WO2000015632 A1 WO 2000015632A1 EP 9906475 W EP9906475 W EP 9906475W WO 0015632 A1 WO0015632 A1 WO 0015632A1
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Prior art keywords
alkyl
alkoxy
optionally substituted
chlorine
fluorine
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PCT/EP1999/006475
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German (de)
English (en)
Inventor
Folker Lieb
Reiner Fischer
Jörg Stetter
Thomas Bretschneider
Christoph Erdelen
Ulrike Wachendorff-Neumann
Original Assignee
Bayer Aktiengesellschaft
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Publication date
Priority claimed from DE19921157A external-priority patent/DE19921157A1/de
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU57450/99A priority Critical patent/AU5745099A/en
Publication of WO2000015632A1 publication Critical patent/WO2000015632A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/32—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655363—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a six-membered ring

Definitions

  • the present invention relates to new thiopyrone derivatives, several processes for their preparation and their use as pesticides and herbicides.
  • V represents hydrogen, halogen, alkyl or alkoxy
  • W represents hydrogen, cyano, nitro, halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio,
  • X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy,
  • Y for hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy,
  • Y and Z together with the carbon atoms to which they are attached represent an optionally substituted and optionally interrupted by one or more heteroatoms or carbonyl
  • W and Z together with the carbon atoms to which they are attached represent an optionally substituted and optionally interrupted by one or more heteroatoms or carbonyl
  • Alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl represents in each case saturated or unsaturated and optionally substituted cycloalkyl or heterocyclyl or for aryl, arylalkyl or hetaryl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano and / or nitro ,
  • D represents hydrogen or an optionally substituted radical from the
  • a and D together with the atoms to which they are attached represent an optionally substituted carbocycle or heterocycle
  • G represents hydrogen, a metal ion equivalent, an ammonium ion, an alkylammonium ion or a group of the formula
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • Rl for alkyl or alkenyl optionally substituted by halogen
  • Cycloalkyl or heterocyclyl or represents in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
  • R2 represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
  • R3, R4 and R ⁇ independently of one another each represent optionally substituted by halogen alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent optionally substituted phenyl, phenoxy or phenylthio, and
  • R "and R 'independently of one another represent hydrogen, each represent optionally substituted by halogen alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted phenyl or benzyl, or together with the N atom to which they are attached, one optionally form oxygen or sulfur-containing optionally substituted cycle.
  • the compounds of the formula (I) can be present in different compositions as geometric and / or optical isomers or isomer mixtures, which may or may not be in a conventional manner and ways can be separated.
  • the present invention relates to both the pure isomers and mixtures of isomers. In the following, however, for the sake of simplicity, we always speak of thiopyrone derivatives of the formula (I), although this means both the pure isomers and, if appropriate, mixtures with different proportions of isomers.
  • the thiopyrone derivatives according to the invention can be derived from the two tautomeric forms (Ia) and (Ia ') and thus as compounds of the formula
  • the thiopyrone derivatives according to the invention can be present either as mixtures of compounds of the formulas (I) and (I ') or in the form of pure isomers. Mixtures of compounds of the formulas (I) and (_ ') can be separated physically, for example by chromatic methods.
  • the formula (I) comprises thiopyrone derivatives of the following structures:
  • X, Y, Z, Rl, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the meanings given above and
  • E represents a metal ion equivalent, an alkylammonium or an ammonium ion.
  • A, D, V, W, X, Y and Z have the meanings given above,
  • Benzyloxy, or two adjacent radicals together represent C 3 -C ß- alkanediyl
  • n stands for integers from 0 to 3
  • V, W, X, Y and Z have the meanings given above and
  • A, D, V, W, X, Y, Z and R 1 have the meanings given above,
  • A, D, V, W, X, Y and Z have the meanings given above, either
  • R 1 has the meaning given above and
  • R 1 has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  • A, D, L, M, V, W, X, Y, Z and R 2 have the meanings given above,
  • A, D, V, W, X, Y and Z have the meanings given above,
  • chloroformic acid (thio) esters of the formula R 2 - M— C— Cl
  • R 2 , L and M have the meanings given above,
  • A, D, V, W, X, Y, Z and R 3 have the meanings given above,
  • A, D, V, W, X, Y and Z have the meanings given above,
  • R 3 has the meaning given above
  • A, D, L, V, W, X, Y, Z, R 4 and R 5 have the meanings given above,
  • A, D, V, W, X, Y and Z have the meanings given above,
  • R 4 and R 5 have the meanings given above and
  • A, D, V, W, X, Y and Z have the meanings given above and
  • E represents a metal ion equivalent, an ammonium ion or an alkylammonium ion,
  • A, D, V, W, X, Y and Z have the meanings given above,
  • R 8 represents hydrogen or alkyl having 1 to 8 carbon atoms
  • R 9 , R 10 and R 1 1 independently of one another represent hydrogen or alkyl
  • A, D, L, V, W, X, Y, Z, R 6 and R 7 have the meanings given above.
  • A, D, V, W, X, Y and Z have the meanings given above,
  • Formula (I) is better than pesticides and herbicides than the most similar, previously known substances with the same direction of action.
  • the thiopyrone derivatives according to the invention are generally defined by the formula (I).
  • V preferably represents hydrogen, halogen, C ⁇ -Cg-alkyl or C ⁇ -Cg-alkoxy.
  • W preferably represents hydrogen, cyano, nitro, halogen, Ci-Cg-alkyl, C 2 - Cg-alkenyl, C2-Cg-alkynyl, Cj-Cg-alkoxy, C ⁇ -C4-haloalkyl, C1-C4-haloalkoxy or in each case phenyl, phenoxy, phenylthio, phenyl-C 4 -C 4 -alkoxy optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, nitro and / or cyano or phenyl-C-C4-alkylthio.
  • X preferably represents halogen, Cj-Cg-alkyl, C2-Cg-alkenyl, C2-Cg-alkynyl,
  • Y preferably represents hydrogen, halogen, Ci-Cg-alkyl, C 1 -Cg-alkoxy, C ⁇ -
  • Z preferably represents hydrogen, halogen, Cj-Cg-alkyl, Cj-Cg-alkoxy, C j -
  • Y and Z are also preferably together for each if appropriate
  • W and Z are also preferably together each C3-C5-alkanediyl or C3-C5-alkenediyl optionally substituted by halogen, Cj-Cg-alkyl, C ⁇ -Cg-alkoxy and / or C ⁇ -C4-haloalkyl, in which optionally one to three members can be replaced independently of one another by oxygen, sulfur, nitrogen or a carbonyl group.
  • A preferably represents hydrogen, each optionally substituted by halogen Ci-C ⁇ alkyl, -C-C ⁇ o-alkoxy-C ⁇ -Cg-alkyl, (poly-Cj-Cg-alkoxy) -Cj-Cg-alkyl or Ci-CiQ -Alkylthio-Ci-Cg-alkyl, for each C3-Cg-cycloalkyl optionally substituted by halogen, Cj-Cg-alkyl and / or C ⁇ -Cg-alkoxy, in which optionally one or two methylene groups by oxygen and / or Sulfur are replaced, or for each phenyl, naphthyl, phenyl-C substituted by halogen, Cj-Cg-alkyl, C ⁇ -Cg-haloalkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, cyano and / or nitro j-Cg-alky
  • D preferably represents hydrogen, in each case optionally substituted by halogen (Poly-Ci-Cg-alkoxy) -C2-Cg-alkyl or C ⁇ -C ⁇ o-alkylthio-C2-Cg-alkyl, for optionally by halogen, C1-C4-alkyl, Cj-C4-alkoxy and / or C ⁇ -C4-haloalkyl substituted C3-Cg-cycloalkyl, in which one or two not directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur, or for each optionally halogen, Cj-Cg-alkyl, Cj-Cg-haloalkyl, C -Cg-alkoxy, C ⁇ -Cg-haloalkoxy, cyano and / or nitro substituted phenyl, hetaryl with 5 or 6 ring atoms and one or two heteroatoms from the series oxygen, sulfur and Nitrogen f, also for
  • a and D also together preferably represent a C3-Cg-alkanediyl
  • C3-Cg-alkenediyl or C4-Cg-alkadienediyl group in each of which a methylene group is optionally replaced by oxygen or sulfur and which are in each case optionally substituted by halogen or in each case optionally substituted by halogen, Cj-Cjo-alkyl or C - Cg-alkoxy , Nitro, cyano, phenyl and / or benzyloxy or by a further C3-Cg-alkanediyl, C3-Cg-alkenediyl or C4-Cg-alkadienediyl group which forms a fused-on ring, in which, if appropriate, one methylene group is substituted by oxygen or Sulfur is replaced and which are optionally substituted by C ⁇ -Cg alkyl.
  • G preferably represents hydrogen, a monovalent metal ion, an equivalent of a divalent metal ion or an ammonium ion of the formula
  • R 9 , R 10 and R 1 1 independently of one another represent hydrogen or alkyl having 1 to 8 carbon atoms, or
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • Ci - C 2 0 alkyl preferably represents in each case optionally halogen-substituted Ci - C 2 0 alkyl, C 2 -C 2 o-alkenyl, Cj-Cg-alkoxy-Cj-Cg-alkyl, C j -CG-alkylthio Cj-Cg-alkyl or (Poly-Cj-Cg-alkoxy) -C ⁇ -Cg-alkyl, or for C3-C - optionally substituted by halogen, Cj-Cg-alkyl and / or C ⁇ -Cg-alkoxy -
  • Cycloalkyl in which one or two not directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur,
  • hetaryloxy-Cj-Cg-alkyl optionally substituted by halogen, amino and / or C ⁇ -Cg-alkyl and having one or two heteroatoms from the series oxygen, sulfur and nitrogen.
  • R 2 preferably represents in each case optionally substituted by halogen Ci - C o-alkyl, C 2 -C 2 o-alkenyl, -C-Cg-alkoxy-C 2 -Cg-alkyl or (poly- -Cg-alkoxy) -C - Cg alkyl,
  • C3-Cg-cycloalkyl which is optionally substituted by halogen, Cj-Cg-alkyl and / or C ⁇ -Cg-alkoxy or
  • R 3 preferably represents Ci-Cg-alkyl optionally substituted by halogen or in each case optionally by halogen, C [-Cg-alkyl, C ⁇ -Cg-alkoxy,
  • R 4 and R5 independently of one another preferably represent in each case optionally substituted by halogen C 1 -C 6 -alkyl, C 6 -C 6 -alkoxy, C 1 -C 6 -alkylamino, di- (C] -Cg-alkyl) -amino, Cj- Cg-alkylthio or C3-Cg-alkenylthio, or for each optionally by halogen, nitro, cyano, Cj-C4-alkoxy, C ⁇ -C4-haloalkoxy, C ⁇ -C4-alkylthio, C ⁇ -C4-haloalkylthio, C1-C4- Alkyl and / or C ⁇ -C4-haloalkyl substituted phenyl, phenoxy or phenylthio.
  • R ⁇ and Rl independently of one another preferably represent hydrogen, each of which is optionally substituted by halogen-Ci-Cg-alkyl, C3-Cg-cycloalkyl, C ⁇ -Cg-alkoxy, C3-Cg-alkenyl or -C-Cg-alkoxy- C2-Cg-alkyl, for phenyl or benzyl which are each optionally substituted by halogen, C ⁇ -Cg-alkyl, Cj-Cg-haloalkyl and or Ci-Cg-alkoxy or together for a C3- which is optionally substituted by C ⁇ -Cg-alkyl C - alkylene radical in which a methylene group is optionally replaced by oxygen or sulfur.
  • V particularly preferably represents hydrogen.
  • W particularly preferably represents hydrogen, cyano, nitro, fluorine, chlorine, bromine, C r C 4 alkyl, C r C 4 alkoxy, C r C 2 haloalkyl or C ] ⁇ haloalkoxy.
  • X particularly preferably represents fluorine, chlorine, bromine, C1-C4- alkyl, C1-C4-
  • Y particularly preferably represents hydrogen, fluorine, chlorine, bromine, C 1 -C 4 -alkyl
  • Z particularly preferably represents hydrogen, fluorine, chlorine, bromine, C 4 -C 4 -alkyl,
  • D particularly preferably represents hydrogen, each optionally substituted by fluorine or chlorine, Ci-Cio-alkyl, -C-Cg-alkoxy-C2-Cg-alkyl, or Cj-Cg-alkylthio-C2-Cg-alkyl, optionally by fluorine , Chlorine, C1-C4-alkyl, -CC-C4-alkoxy and / or -C-C2-haloalkyl substituted C3-C7-cycloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur, or for each optionally by fluorine, chlorine, Bromine, -CC 4 -alkyl, ⁇ -haloalkyl, C ⁇ -C4-alkoxy, C ⁇ -
  • a and D together also particularly preferably represent a C3-C5
  • Alkanediyl or C3-C5-alkenediyl group in which in each case one carbon atom is optionally replaced by oxygen or sulfur and which are optionally substituted by fluorine, chlorine or by C ⁇ -Cg-alkyl or Cj-C4-alkoxy which are optionally substituted by fluorine or chlorine , or for a possibly by C ! -C 4 alkyl, fluorine, chlorine, Bromine, C] -C 4 alkoxy, C 1 -C 2 haloalkyl, C] -C 2 haloalkoxy, cyano and / or nitro substituted C 4 alkane dienyl group.
  • G particularly preferably represents hydrogen, an alkali metal ion, an equivalent of an alkaline earth metal ion or an ammonium ion of the formula
  • R 9 , R 10 and R independently of one another represent hydrogen or alkyl having up to 6 carbon atoms, or
  • L represents oxygen or sulfur
  • M stands for oxygen or sulfur.
  • Rl particularly preferably represents in each case optionally substituted by fluorine or chlorine Cj-Cig-alkyl, C2-C ⁇ g-alkenyl, Cj-Cg-alkoxy-Ci-Cg-alkyl, Ci-Cg-alkylthio-Cj-Cg-alkyl or (poly -C ⁇ -Cg-alkoxy) -C 1 -Cg-alkyl or for optionally by fluorine, chlorine, Cj-Cf-alkyl and / or Cj-C5-alkoxy substituted C3-C7-cycloalkyl, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
  • phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, C 1 -haloalkyl, C 3 -haloalkoxy, C 1 -C 4 -alkylthio and / or C 1 -C 4 -alkylsulfonyl ,
  • phenyl-C1-C which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C 1 -C4-alkoxy, C1-C3 -haloalkyl and / or C1-C3 -haloalkoxy . 4-a.kyl.
  • R 2 particularly preferably represents C 1 -C 8 -alkyl, C 2 -C 1 g-alkenyl, C 1 -C 6 -alkoxy-C2-Cg-alkyl or (poly-C 1 -Cg-alkoxy) -C 2, each optionally substituted by fluorine or chlorine -Cg-alkyl,
  • C3-C7-cycloalkyl optionally substituted by fluorine, chlorine, Cj-C4-alkyl and / or Cj-C4-alkoxy or
  • phenyl or benzyl each optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, -C-C3-alkoxy, C ⁇ -C3-haloalkyl and / or C1-C3 -haloalkoxy.
  • R 3 particularly preferably represents C 1 -C 6 -alkyl optionally substituted by fluorine or chlorine, or in each case optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 2 haloalkoxy, C1 - C2- haloalkyl, cyano and / or nitro substituted phenyl or benzyl.
  • R 1 and R 5 independently of one another particularly preferably each represent C 1 -C 6 -alkyl which is optionally substituted by fluorine or chlorine, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylamino, di- (C 1 -C 6 -alkyl) amino, C ⁇ -Cg-alkylthio or C3-C4-alkenylthio or for each optionally by fluorine, chlorine, bromine, nitro, cyano, Cj-C3-A_koxy, C1-C3-Ha.ogena.koxy, C ⁇ -C3-alkylthio, C ⁇ -
  • R6 and R? independently of one another particularly preferably represent hydrogen, represent in each case optionally substituted by fluorine or chlorine, C j -CG alkyl,
  • V very particularly preferably represents hydrogen.
  • W very particularly preferably represents hydrogen, cyano, nitro, fluorine, chlorine,
  • Bromine methyl, ethyl, propyl, butyl, iso-propyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, difluoromethoxy or trifluoromethoxy.
  • X very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl,
  • Y very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, Propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy or cyano.
  • Z very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isobutyl, isopropyl, tert-butyl, methoxy, ethoxy,
  • D very particularly preferably represents hydrogen, in each case optionally substituted by fluorine or chlorine, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C2-C4-alkyl, C i -C4-alkylthio-C2-C4-alkyl or C3- Cg-cycloalkyl in which a methylene group is optionally replaced by oxygen or sulfur, or in each case optionally by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano and / or nitro substituted phenyl, pyridyl, thienyl or benzyl.
  • a and D are also particularly preferred for a C3-C5-
  • Alkanediyl or C3-C5-alkenediyl group in which in each case one methylene group is optionally replaced by oxygen or sulfur, and which are optionally substituted by C ) -C 4 alkyl or CC 4 - alkoxy, or for one optionally by methyl, ethyl, propyl , Isopropyl, tert-butyl, methoxy, ethoxy, iso-propoxy, n-propoxy, tert-butoxy, trifluoromethyl, Difluoromethoxy, trifluoromethoxy, cyano and / or nitro substituted alkadienediyl group.
  • G very particularly preferably represents hydrogen, a lithium, sodium or potassium ion, an equivalent of a magnesium or calcium ion or a
  • R 9 , R 10 and R 1 1 independently of one another represent hydrogen or alkyl having 1 to 4 carbon atoms, or
  • G very particularly preferably represents a group of the formula
  • L represents oxygen or sulfur
  • M stands for oxygen or sulfur.
  • R very particularly preferably represents C 1 -C 4 -alkyl, C 2 -C 14 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C, each optionally substituted by fluorine or chlorine 1 -Cg-alkyl, (poly-C 1 -C -alkoxy) -C 1 -C 4 -alkyl or for C3-Cg- optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, methoxy, ethoxy, n-propoxy and / or isopropoxy Cycloalkyl, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
  • phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl and / or ethylsulfonyl,
  • benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
  • R2 very particularly preferably represents C 1 -C 14 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -alkoxy-C2-Cg-alkyl or (poly-C 1 -C 4 -alkoxy) which is optionally substituted by fluorine or chlorine, C2-Cg-alkyl,
  • C3-Cg-cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl and / or methoxy,
  • R 3 very particularly preferably represents methyl, ethyl, propyl, isopropyl, butyl, tert-butyl which is optionally substituted by fluorine or chlorine, or represents in each case optionally by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, cyano and / or nitro substituted phenyl or benzyl.
  • R4 and R5 independently of one another very particularly preferably represent in each case optionally substituted by fluorine or chlorine -CC4-alkyl, C1-C4-
  • R6 and R 7 independently of one another very particularly preferably represent hydrogen, in each case optionally substituted by fluorine or chlorine, C1-C4-alkyl, C 3 -Cg-cycloalkyl, C 1 -C4-alkoxy, C 3 -C4-alkenyl or C ⁇ -Alk-oxy-C2-C4-alkyl, for phenyl or benzyl optionally substituted in each case by fluorine, chlorine, bromine, methyl, methoxy and / or trifluoromethyl, or together for a C5-Cg-alkylene radical optionally substituted by methyl or ethyl, in which may replace a methylene group with oxygen or sulfur.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also be used in connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.
  • Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitutions the substituents can be the same or different. “Multiple” substituted radicals are preferably to be understood as radicals which carry two or three substituents.
  • Process (C) can be illustrated by the following reaction scheme.
  • Formula (II) provides a general definition of the thiocarbonyl compounds required as starting materials in process (A, variant ⁇ ) according to the invention.
  • a and D preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the thiopyrone derivatives of the formula (I) according to the invention.
  • the thiocarbonyl compounds of the formula (I) are known or can be prepared by known processes.
  • Formula (III) provides a general definition of the thiophenols required as starting materials in process (A, variant ⁇ ) according to the invention. In this formula it says
  • Q preferably for fluorine, chlorine, bromine, C j -C 4 alkyl, C r C 4 alkoxy, CC 2 - haloalkyl, C 1 -C 2 haloalkoxy, cyano and nitro and
  • n preferably represents integers from 0 to 3
  • Q particularly preferably represents methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, iso-propoxy, n-propoxy, tert-butoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano and nitro, and
  • n particularly preferably represents the numbers 0, 1 and 2,
  • At least one ortho position to the mercapto group is unsubstituted.
  • the thiophenols of the formula (III) are known or can be prepared by known methods.
  • Formula (IV) provides a general definition of the ketene derivatives required as reaction components when carrying out process (A) according to the invention.
  • V, W, X, Y and Z preferably have those meanings which are already in connection with the description of the invention
  • Thiopyrone derivatives of the formula (I) were mentioned as preferred for these radicals.
  • Shark also preferably represents chlorine or bromine.
  • ketene derivatives of the formula (IV) are known or can be prepared by known processes (cf. Org. Prep. Proced. Int. 7, 155-158 (1975) and DE-A
  • V, W, X, Y and Z have the meanings given above,
  • acid halides such as, for example, thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, oxalyl chloride, phosgene or thionyl bromide, if appropriate in the presence of catalysts, such as, for example, diethylformamide, methylstylformamide or triphenylphosphine and, if appropriate, in the presence of bases such as, for example Pyridine or triethylamine, at a temperature between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
  • acid halides such as, for example, thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, oxalyl chloride, phosgene or thionyl bromide
  • catalysts such as, for example, diethylformamide, methylstylformamide or triphenylphosphine and,
  • substituted phenylmalonic acids of the formula (XIV) are known or can be prepared by known methods (cf., for example, Organikum, VEB Deutscher Verlag dermaschineen, Berlin 1977, p. 517 ff). Substituted phenylmalonic acids of the formula (XIV) are thus obtained by using substituted phenylmalonic esters of the formula in which
  • V, W, X, Y and Z have the meanings given above and
  • R 12 represents alkyl having 1 to 4 carbon atoms
  • alkali metal hydroxides such as sodium hydroxide or potassium hydroxide
  • a diluent such as water
  • V, W, X, Y and Z preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the thiopyrone derivatives of the formula (I) according to the invention.
  • R 12 preferably represents methyl or ethyl.
  • substituted phenylmalonic acid esters of the formula (XV) are known or can be prepared by known methods (cf. Tetrahedron Letters 27, 2763 (1986) and VEB Deutscher Verlag dermaschineen, Berlin 1977, p. 587 ff.).
  • the thiopyrone derivatives of the formula (Ia) required as starting materials for carrying out processes (B), (C), (D), (E), (F) and (G) are compounds according to the invention which can be obtained by the process according to the invention Have (A) made.
  • Shark 'and shark 2 also preferably represent chlorine or bromine.
  • Me is preferably a monovalent metal ion or an equivalent of a divalent metal ion.
  • R 8 preferably represents hydrogen or alkyl having 1 to 6 carbon atoms.
  • R 9 , R 10 and R 1 'independently of one another are preferably hydrogen or alkyl having 1 to 8 carbon atoms.
  • Me particularly preferably represents an alkali metal ion or an equivalent of one
  • R 8 particularly preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.
  • R 9 , R 10 and R 1 1 independently of one another particularly preferably represent hydrogen or alkyl having 1 to 6 carbon atoms.
  • Me very particularly preferably represents a lithium, sodium or potassium ion, an equivalent of a calcium or magnesium ion.
  • R 8 very particularly preferably represents hydrogen, methyl, ethyl or tert-butyl.
  • R 9 , R 10 and R 1 'independently of one another very particularly preferably represent hydrogen or alkyl having 1 to 4 carbon atoms.
  • the compounds of the formulas (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII) are known or can be prepared by known methods.
  • Suitable diluents for carrying out process (A) according to variants ( ⁇ ) and ( ⁇ ) are all customary organic solvents which are inert to the reactants.
  • Hydrocarbons such as o-dichlorobenzene, tetralin, toluene and xylene, preferably ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, and also polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or N-methylpyrrolidone are preferably usable.
  • Suitable acid acceptors when carrying out process (A) according to variants ( ⁇ ) and ( ⁇ ) are all customary acid binders.
  • Tertiary amines such as triethylamine, pyridine,
  • Diazabicyclooctane (DABCO), Diazabicycloundecen (DBU), Diazabicyclononen (DBN), Hünig-Base or N, N-Dimethyl-aniline.
  • reaction temperatures can be varied within a substantial range. It is expedient to work at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 220 ° C.
  • the process is preferably carried out under atmospheric pressure.
  • ( ⁇ ) and ( ⁇ ) are generally 1 mol of thiocarbonyl compounds of the formula (II) or of thiophenol of the formula (III) an equimolar amount of ketene derivative of the formula (IV) and optionally also an equimolar amount on acid accept one.
  • Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin are preferably usable, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ketones such as acetone and methylisopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and Dioxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can also be carried out in the presence of water.
  • the acid binders used in the reaction are those according to the invention.
  • Process (B, variant ⁇ ) all customary acid acceptors into consideration.
  • Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hunig base and N, N-dimethylaniline, and also alkaline earth metal oxides, such as magnesium and calcium oxide, are also preferably used Alkali and alkaline earth metal carbonates, such as sodium carbonate,
  • Potassium carbonate and calcium carbonate as well as alkali hydroxides, such as sodium hydroxide and potassium hydroxide.
  • reaction temperatures can be varied within a relatively wide range. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
  • the starting materials of the formula (Ia) acid halide of the formula (V) are generally in each case used in approximately equivalent amounts. However, it is also possible use the acid halide in a large excess (up to 5 mol). The processing takes place according to usual methods.
  • the diluents used in the process (B, variant ⁇ ) according to the invention are preferably those which are also suitable for the
  • the acid binders which are optionally added in process (B, variant ⁇ ) are preferably those acid binders which are also preferred when using acid halides.
  • reaction temperatures can be varied within a substantial range in the process according to the invention (B, variant ⁇ ). In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
  • Process (B) according to the invention is also preferably carried out under atmospheric pressure.
  • the starting materials of the formula (Ia) and the carboxylic anhydride of the formula (VI) are generally used in approximately equivalent amounts. However, it is also possible to use the carboxylic anhydride in a larger excess (up to 5 mol).
  • the processing takes place according to usual methods. The general procedure is to remove the diluent and excess carboxylic anhydride and the carboxylic acid formed by distillation or by washing with an organic solvent or with water.
  • Suitable acid binders in process (C) according to the invention are all customary acid acceptors.
  • Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and N, N-dimethylaniline, furthermore alkaline earth metal oxides such as magnesium and calcium oxide, and also alkali and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal alcoholates such as sodium methylate and potassium tert-butoxide
  • alkali metal hydrides such as sodium hydride
  • Suitable diluents for carrying out process (C) according to the invention are all customary inert solvents.
  • Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin are preferably usable, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, in addition
  • Ketones such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic acid esters, such as ethyl acetate, also nitriles, such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide and sulfolane.
  • carboxylic acid esters such as ethyl acetate
  • nitriles such as acetonitrile
  • strongly polar solvents such as dimethylformamide, dimethyl sulfoxide and sulfolane.
  • the addition of strong deprotonating agents such as e.g. Sodium hydride or potassium tert-butylate is the enolate salt of the compound of formula (Ia), the further addition of acid binders can be dispensed with.
  • reaction temperatures can also be varied within a relatively wide range when carrying out process (C) according to the invention.
  • temperatures between -20 ° C and + 120 ° C, preferably between 0 ° C and 60 ° C.
  • the process (C) according to the invention is generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.
  • Thiopyrone derivative of the formula (Ia) in general an equimolar amount of chloroformic acid (thio) ester of the formula (VII). However, it is also possible to use one or the other component in a larger excess (up to 2 mol).
  • the processing takes place according to usual methods. In general, one proceeds by removing precipitated salts and passing through the remaining reaction mixture
  • Suitable diluents for carrying out process (D) according to the invention are all customary inert, organic solvents.
  • Ethers such as tetrahydrofuran, amides such as dimethylformamide, ketones, carboxylic acid esters, nitriles, sulfones, sulfoxides such as dimethyl sulfoxide, and also halogenated hydrocarbons such as methylene chloride are preferably usable.
  • Suitable acid binders for carrying out process (D) according to the invention are all customary inorganic or organic bases. Examples include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, sodium hydride and potassium tert-butoxide.
  • the enolate salt of the compound of the formula (Ia) is prepared by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butylate), the further addition of acid binders can be dispensed with.
  • strong deprotonating agents such as, for example, sodium hydride or potassium tert-butylate
  • reaction temperatures can also be varied within a relatively wide range when carrying out process (D) according to the invention.
  • NEN is carried out at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 70 ° C.
  • the process (D) according to the invention is generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.
  • Suitable diluents for carrying out process (E) according to the invention are all customary inert, organic solvents.
  • Ethers such as tetrahydrofuran, amides, such as dimethylformamide, and also ketones, carboxylic acid esters, nitriles, such as acetonitrile, and also sulfones and sulfoxides, can preferably be used.
  • dimethyl sulfoxide and also halogenated hydrocarbons, such as methylene chloride.
  • Suitable acid binders when carrying out process (E) according to the invention are all customary inorganic or organic bases. Examples include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
  • reaction temperatures can also be varied within a relatively wide range when carrying out process (E) according to the invention.
  • temperatures between -40 ° C and + 150 ° C, preferably between -10 ° C and +1 10 ° C.
  • the process (E) according to the invention is generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.
  • Thiopyrone derivative of formula (Ia) generally 1 to 2 moles, preferably 1 to 1.3 moles of phosphorus compound of formula (IX).
  • the processing takes place according to the usual methods of organic chemistry.
  • the end products are preferably purified by crystallization, chromatographic purification or by so-called “distillation", i.e. removal of the volatile constituents under reduced pressure.
  • Suitable diluents for carrying out process (F) according to variants ( ⁇ ) and ( ⁇ ) are all organic solvents customary for such reactions and also water. Are preferably usable
  • Ethers such as tetrahydrofuran, dioxane and diethyl ether, furthermore alcohols, such as methanol, ethanol and isopropanol, and also water.
  • reaction temperatures can also be varied within a substantial range. In general, temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.
  • ( ⁇ ) and (ß) are generally based on 1 mol of thiopyrone derivative of the formula (Ia) 1 to 2 mol or a larger excess of metal compounds Formula (X) or an amine of formula (XI).
  • the processing takes place according to usual methods.
  • Suitable diluents for carrying out process (G) according to variants ( ⁇ ) and ( ⁇ ) are all customary inert, organic solvents.
  • Ethers such as tetrahydrofuran, amides such as dimethylformamide, ketones, carboxylic acid esters, nitrites, sulfones, sulfoxides such as dimethyl sulfoxide, and also halogenated hydrocarbons such as methylene chloride can preferably be used.
  • Suitable catalysts for carrying out process (G) according to variant () are all reaction accelerators customary for such reactions.
  • Organic tin compounds, such as dibutyltin dilaurate, can preferably be used.
  • Suitable acid binders for carrying out process (G) according to variant ( ⁇ ) are all customary inorganic or organic bases. Examples include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine, sodium hydride and potassium tert-butoxide.
  • reaction temperatures can be varied within a substantial range.
  • temperatures between 0 ° C and + 150 ° C, preferably between 20 ° C and 70 ° C.
  • the thiopyrone derivatives of the formula (I) according to the invention have very good pesticidal activity and are very well tolerated by crop plants.
  • the active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • Pests include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Collembola e.g. Onychiurus armatus.
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Thysanoptera e.g. Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi, Thrips tabaci.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosi- phum avenae, Myzus spp., Phoroponasum.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosi- phum avenae, Myzus spp., Phoroponasum.
  • Euscelis bilobatus Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodel- phax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
  • Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, LithocoUetis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Der- manyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipice- phalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp. rioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the active compounds according to the invention are notable for high insecticidal and acaricidal activity after leaf and soil use. They can be used with particularly good success for combating plant-damaging insects, for example against the larvae of the horseradish leaf beetle (Phaedon cochleariae), against the larvae of the green leafhopper (Nephotettix cincticeps) and against the larvae of the green peach aphid (Myzus persicae).
  • the active compounds according to the invention also have a herbicidal activity and can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the dosages of the active compounds according to the invention required for weed control are between 0.001 and 10 kg / ha, preferably between 0.005 and 5 kg / ha.
  • the active compounds according to the invention can e.g. can be used in the following plants:
  • the thiopyrone derivatives of the formula (I) according to the invention also have a fungicidal action.
  • they can be used to control Erysiphe granimis or against Pyricularia oryzae on rice.
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops e.g. Forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective weeds - combat can be used in annual crops.
  • the active compounds according to the invention are very suitable for the selective control of monocotyledon weeds experienced in dicotyledon crops in the pre- and post-run. For example, they can be used in cotton or sugar beet with very good results to control harmful grasses.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifiers and / or foam-generating agents are: for example nonionogenic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfonates fates,
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% and in addition preferably extenders and / or surface-active agents.
  • the active compounds according to the invention can be present in commercially available formulations and in the use forms prepared from these formulations, in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nemicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • Pha- (o-tolyloxy) -o-tolyl] acetate 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
  • Bacillus thuringiensis Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim,
  • Cadusafos Carbaryl. Carboftiran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron,
  • Chlormephos Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofen- tezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,
  • Lambda cyhalothrin Lufenuron, Malathion, Mecarbam. Mevinphos, Mesulfenphos. Metaldehyde, methacrifos, methamidophos, methidathione, methiocarb, methomyl, metolcarb. Milbemectin, Monocrotophos, Moxidectin,
  • Tebufenozid Tebufenpyrad
  • Tebupirimiphos Teflubenzuron, Tefluthrin, Temephos
  • Herbicides for example anilides, e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2.4
  • Aryloxy phenoxy alkanoic acid esters such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl;
  • Azinones such as chloridazon and norflurazon;
  • Carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham;
  • Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor;
  • Dinitroanilines such as oryzalin, pendimethalin and trifluralin;
  • Diphenyl ethers such as acifluorfen, bifenox, fluoroglycopene, fomesafen, hal
  • Imazaquin Nitrites, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialates,
  • EPTC Esprocarb, Molinate, Prosulfocarb, Thiobencarb and Triallate; Triazines, e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones such as e.g.
  • Others such as Aminotriazole, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
  • the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are connections through which the
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the drug concentration of the Application forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active substances When used against hygiene pests and pests of stored products, the active substances are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair linge, featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair linge, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
  • Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,
  • Phlebotomus spp. Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musa spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp ., Hippobosca spp., Lipoptena spp., Melophagus spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp.,
  • Otodectes spp. Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats,
  • Combating these arthropods is said to prevent deaths and reduced performance (in meat, milk, wool, skins, eggs, honey, etc.) be reduced, so that more economical and simple animal husbandry is possible through the use of the active compounds according to the invention.
  • the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets,
  • parenteral administration such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal Application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the aid of shaped articles containing active ingredients, such
  • formulations for example powders, emulsions, flowable agents
  • active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10,000 times dilution, or use them as a chemical bath.
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinisis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints.
  • the one to be protected against insect attack is very particularly preferably
  • Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, boat jetties,
  • the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents.
  • the organic chemical solvents used are preferably oily or oily ones
  • Corresponding mineral oils are used as such low-volatility, water-insoluble, oily and oily solvents or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene.
  • Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous.
  • Turpentine oil and the like are advantageous.
  • liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably - monochloronaphthalene, are used .
  • the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and has a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture.
  • Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.
  • the organic-chemical binders used are the water-dilutable substances known per se and / or in the ores used.
  • ganisch-chemical solvents soluble or dispersible or emulsifiable synthetic resins and or binding drying oils in particular binders consisting of or containing an acrylate resin, a vinyl resin, eg polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, Hydrocarbon resin such as indene
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
  • binder All or part of the binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to volatilize the active ingredients and crystallize or precipitate! prevent. They preferably replace 0.01 to 30% of the binder (based on
  • the plasticizers come from the chemical classes of phthalic acid esters such as
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as butyl stearate or Amyl stearate
  • oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumazole, as well as fungonazole, as well as fungonazole, as well as fungonazole, as well as Fungazazole, as well as Fungazazole, like Fungazazole Tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanide, tolylfluanid, 3-iodine
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper (Nephettettix cincticeps) while the seedlings are still moist.
  • the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentrations.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish beetle (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by dipping into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella xylostella) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Solvent 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Bean plants Phaseolus vulgaris
  • Tetranychus urticae which are heavily infested with all stages of the common spider mite (Tetranychus urticae)
  • an active ingredient preparation of the desired concentration is sprayed with an active ingredient preparation of the desired concentration.
  • the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no cicadas have been killed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne de nouveaux dérivés de thiopyrone de formule (I), dans laquelle A, D, G, V, W, X, Y et Z ont la signification indiquée dans la description. L'invention concerne également plusieurs procédés pour préparer ces substances et l'utilisation de ces dernières comme pesticides et herbicides.
PCT/EP1999/006475 1998-09-11 1999-09-03 Derives de thiopyrone et leur utilisation comme pesticides WO2000015632A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57450/99A AU5745099A (en) 1998-09-11 1999-09-03 Thiopyron-derivative and their use as pesticides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19841511.7 1998-09-11
DE19841511 1998-09-11
DE19921157.4 1999-05-07
DE19921157A DE19921157A1 (de) 1998-09-11 1999-05-07 Thiopyron-Derivate

Publications (1)

Publication Number Publication Date
WO2000015632A1 true WO2000015632A1 (fr) 2000-03-23

Family

ID=26048785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/006475 WO2000015632A1 (fr) 1998-09-11 1999-09-03 Derives de thiopyrone et leur utilisation comme pesticides

Country Status (2)

Country Link
AU (1) AU5745099A (fr)
WO (1) WO2000015632A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988004652A1 (fr) * 1986-12-17 1988-06-30 Nippon Soda Co., Ltd. Composes heterocycliques possedant un squelette triketo
EP0588137A1 (fr) * 1992-09-10 1994-03-23 Bayer Ag Dérivés de la 3-aryl-pyrane-2-one
WO1997016436A1 (fr) * 1995-10-27 1997-05-09 Bayer Aktiengesellschaft Derives 3-aryl-5-halogeno-pyrone utilises comme pesticides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988004652A1 (fr) * 1986-12-17 1988-06-30 Nippon Soda Co., Ltd. Composes heterocycliques possedant un squelette triketo
EP0588137A1 (fr) * 1992-09-10 1994-03-23 Bayer Ag Dérivés de la 3-aryl-pyrane-2-one
WO1997016436A1 (fr) * 1995-10-27 1997-05-09 Bayer Aktiengesellschaft Derives 3-aryl-5-halogeno-pyrone utilises comme pesticides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
B. SUCHARITS REDDY ET. AL.: "Synthesis of 8,9-Oxygenated 1-Thiocoumestans", INDIAN JOURNAL OF CHEMISTRY, SECTION B, vol. 24B, May 1985 (1985-05-01), pages 556 - 9, XP002126368 *
H. J. TEAGUE ET. AL.: "Thiapyrone Chemistry. III. The Reaction of 2,6-Dimethylthio-3,5-diphenylthiapyrone with Hydroxide Ion.", JOURNAL OF ORGANIC CHEMISTRY, vol. 35, no. 6, June 1970 (1970-06-01), pages 1968 - 70, XP002126369 *

Also Published As

Publication number Publication date
AU5745099A (en) 2000-04-03

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